Multi-step method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates

Claim 1

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin or enamel an aqueous solution or solutions comprising (1) at least on acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin or enamel surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with calcium and which contains at least one carboxyl group; and (2) acid; (b) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)gylcine and glycidyl methacrylate, and (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate in a solvent; and (c) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, and (3) 4-methacryloxyethyltrimellitic anhydride.

Claim 2

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin or enamel an aqueous solution or solutions comprising (1) at least on acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin or enamel surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with calcium and which contains at least one carboxyl group; and (2) acid; (b) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)gylcine and glycidyl methacrylate, and (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate in a solvent; and (c) contacting with the surface of the dentin or enamel a solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate, (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate, and (3) 4-methacryloxyethyltrimellitic anhydride.

Claim 13

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting the surface of the dentin or enamel with an aqueous solution comprising ferric oxalate and nitric acid; (b) washing and then drying the surface of the dentin or enamel; (c) contacting the surface of the dentin or enamel with a first acetone solution comprising at least one compound selected frorm the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, and (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate in acetone; (d) removing any excess of the first acetone solution and rinsing the surface of the dentin or enamel with acetone, removing any excess acetone and drying the surface; (e) contacting the surface of the dentin or enamel with a second acetone solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate and (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate.

Claim 14

A method for preparing the surface of dentin or enamel for adhesion of composite materials or resins, which method comprises: (a) contacting the surface of the dentin or enamel with an aqueous solution comprising ferric oxalate and nitric acid; (b) washing and then drying the surface of the dentin or enamel; (c) contacting the surface of the dentin or enamel with a first acetone solution comprising at least one compound selected frorm the group consisting of (1) N-phenylglycine, (2) the adduct of N(p-tolyl)glycine and glycidyl methacrylate, and (3) the addition reaction product of N-phenylglycine and glycidyl methacrylate in acetone; (d) removing any excess of the first acetone solution and rinsing the surface of the dentin or enamel with acetone, removing any excess acetone and drying the surface; (e) contacting the surface of the dentin or enamel with a second acetone solution comprising at least one compound selected from the group consisting of (1) the addition reaction product of pyromellitic acid dianhydride and 2-hydroxyethyl methacrylate and (2) the addition reaction product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 2-hydroxyethyl methacrylate.

Claim 26

A method for preparing the surface of dentin, enamel or industrial substrates for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin, enamel or industrial substrate an aqueous solution or solutions comprising (1) at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin, enamel, or industrial substrate surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with cations of the substrate surface and which contains at least one carboxyl group; and (2) acid; (b) contacting with the surface of the dentin, enamel or industrial substrate a solution comprising a solvent and a surface-active compound of the formula: ##STR12## where: d=0 or 1; m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 12; r=0 to 10; m+p+q=0 to 20; R is selected from the following groups: (a) --O) f (CH 2 ) t H straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (b) --O) f (CH 2 ) t COOH, with t=0 to 12, and with f=0 or 1; (c) --O) f (CH 2 ) d O--H, with d=1 to 12; and with f=0 or 1; and (d) F, Cl, Br and I; and the number of R groups per molecule is 0 to 5, and these R groups are in the para meta, or ortho positions relative to the nitrogen; (c) contacting with the surface of the dentin, enamel, or industrial substrate a solution comprising at least one coupling agent of the formula: ##STR13## where: g=0 to 7; E is a polymerizable moiety: --COO--CH(CH 2 ) j H) q (CHOH) m (CH 2 ) p OCO--C--CH 2 ) r H)═CH 2 ; wherein r=0 or 1; p=0 to 12; m=0 to 6; q=0 to 2; j=0 or 1; p+m+q=2 to 20; the number of E groups per molecule is 1 to 8; A is an anhydride group --OCOCO-- (attached to vicinal ring carbon atoms); the number of A groups per molecule is 0 to 1; X is a halide group; and the number of X groups per molecule is 0 to 8; and y is 0 to 1.

Claim 27

A method for preparing the surface of dentin, enamel or industrial substrates for adhesion of composite materials or resins, which method comprises: (a) contacting with the surface of the dentin, enamel or industrial substrate an aqueous solution or solutions comprising (1) at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin, enamel, or industrial substrate surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with cations of the substrate surface and which contains at least one carboxyl group; and (2) acid; (b) contacting with the surface of the dentin, enamel or industrial substrate a solution comprising a solvent and a surface-active compound of the formula: ##STR12## where: d=0 or 1; m=0 to 6; n=1 to 10; p=0 to 12; q=0 to 12; r=0 to 10; m+p+q=0 to 20; R is selected from the following groups: (a) --O) f (CH 2 ) t H straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12; (b) --O) f (CH 2 ) t COOH, with t=0 to 12, and with f=0 or 1; (c) --O) f (CH 2 ) d O--H, with d=1 to 12; and with f=0 or 1; and (d) F, Cl, Br and I; and the number of R groups per molecule is 0 to 5, and these R groups are in the para meta, or ortho positions relative to the nitrogen; (c) contacting with the surface of the dentin, enamel, or industrial substrate a solution comprising at least one coupling agent of the formula: ##STR13## where: g=0 to 7; E is a polymerizable moiety: --COO--CH(CH 2 ) j H) q (CHOH) m (CH 2 ) p OCO--C--CH 2 ) r H)═CH 2 ; wherein r=0 or 1; p=0 to 12; m=0 to 6; q=0 to 2; j=0 or 1; p+m+q=2 to 20; the number of E groups per molecule is 1 to 8; A is an anhydride group --OCOCO-- (attached to vicinal ring carbon atoms); the number of A groups per molecule is 0 to 1; X is a halide group; and the number of X groups per molecule is 0 to 8; and y is 0 to 1.